CN110590027A - Defluorination method for industrial sewage - Google Patents
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- CN110590027A CN110590027A CN201910829866.6A CN201910829866A CN110590027A CN 110590027 A CN110590027 A CN 110590027A CN 201910829866 A CN201910829866 A CN 201910829866A CN 110590027 A CN110590027 A CN 110590027A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46176—Galvanic cells
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5209—Regulation methods for flocculation or precipitation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5281—Installations for water purification using chemical agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F2001/007—Processes including a sedimentation step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/05—Conductivity or salinity
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/05—Conductivity or salinity
- C02F2209/055—Hardness
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/11—Turbidity
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/29—Chlorine compounds
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
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- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention belongs to the technical field of sewage treatment, and provides a defluorination method for industrial sewage, aiming at solving the problems that the prior fluorine-containing wastewater treated difficultly meets the discharge standard that fluoride is less than or equal to 1mg/L, the electrodialysis method and the electric flocculation method have high power consumption, and the reverse osmosis method has higher requirements on the quality of inlet water and low water yield. Acidifying the sewage before the sewage enters a micro-electrolysis reaction tank, wherein iron carbon is arranged in the micro-electrolysis reaction tank, and compressed air is used for aeration; adding active calcium hydroxide before entering a coagulating sedimentation reaction tank, adjusting the pH value to 8.5-9.5, adding a defluorinating agent into the coagulating sedimentation reaction tank, stirring by an aeration device for reaction, and discharging to a clarification tank; and (4) dropwise adding a flocculating agent before entering the clarification tank, flocculating and settling in the clarification tank, and taking the supernatant for analysis. The concentration of the fluorine ions in the discharged water is below 1 mg/L. The method has the advantages of obvious effect, simple process flow, convenient and reliable control, capability of meeting the requirements of enterprises on reducing the sewage treatment cost, realizing effective removal of fluoride ions and meeting the requirements of enterprise environmental protection and production and operation.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a defluorination method for industrial sewage, which is used for curing and removing fluoride ions of chemical industry, coal-fired power plants, coal mines and other fluorine-containing sewage before the sewage is discharged or recycled, so as to meet the environmental protection requirement of external drainage and the process stability requirement of circulating water.
Technical Field
Fluorine is a trace element necessary for human bodies, is an indispensable substance component for forming hard bones and teeth, can prevent decayed teeth, maintains normal calcium and phosphorus metabolism of human bodies, and improves the anti-aging capability of organisms. However, fluorine poisoning and various adverse effects can occur when the daily fluorine ion intake of a human body is higher than 4 mg.
With the increasing requirements of the national environmental protection, the treatment of the fluorine-containing wastewater is not only the problem of coal chemical industry enterprises and coal mines, but also a new problem and a new challenge to be faced by sewage discharge enterprises of steel, metallurgy, textile, printing and dyeing and the like. The waste water with higher fluoride concentration is treated by combining a plurality of methods to ensure that the fluoride concentration of the effluent is lower than 10mg/L, and the advanced defluorination treatment is needed to meet the condition that the fluoride content is lower than 1 mg/L.
At present, the fluorine-containing wastewater treatment methods are various, and mainly comprise a chemical precipitation method, a coagulating precipitation method, an electrodialysis method, an electric flocculation method, a reverse osmosis method, an ion exchange resin method, an adsorption method and the like. The treatment of high-concentration fluorine-containing wastewater adopts a method combining a chemical precipitation method and a coagulating precipitation method in industry, and the fluorine removal effect can generally meet the condition that fluoride is less than 10 mg/L. And if the emission standard that fluoride is less than or equal to 1mg/L is met, deep fluorine removal treatment is required to be carried out continuously. The electrodialysis method and the electric flocculation method have high power consumption, and the reverse osmosis method has high requirements on the quality of inlet water and low water yield and is less applied to the field of deep defluorination.
Disclosure of Invention
The invention provides a defluorination method for industrial sewage, aiming at solving the problems that the prior fluorine-containing wastewater treated by the method is difficult to meet the discharge standard that fluoride is less than or equal to 1mg/L, the electrodialysis method and the electroflocculation method have high power consumption, the reverse osmosis method has higher requirement on the quality of inlet water and low water yield, and the application in the field of deep defluorination is less.
The invention is realized by the following technical scheme: a defluorination method for industrial sewage water combines micro-electrolysis, chemical precipitation and coagulating precipitation to remove fluorine; acidifying the sewage to a pH value of 3-5 before the sewage enters a micro-electrolysis reaction tank, arranging iron and carbon in the micro-electrolysis reaction tank, and aerating by using compressed air; adding an active calcium hydroxide auxiliary agent before the micro-electrolyzed sewage enters a coagulating sedimentation reaction tank, adjusting the pH value to be 8.5-9.5, adding a defluorinating agent into the coagulating sedimentation reaction tank, stirring by an aeration device for reaction, and discharging to a clarification tank; and (4) dropping a flocculating agent before the treated water enters a clarification tank, performing flocculation sedimentation in the clarification tank, and taking the supernatant for analysis.
The sewage acidification treatment adopts sulfuric acid, hydrochloric acid or other acidic materials.
The sewage acidification treatment is preferably carried out by adopting polymeric ferric sulfate or polymeric aluminum sulfate for acidification.
The iron carbon is semi-coking dry distillation type iron carbon, is added at one time, water enters from the bottom, and the pH value is controlled to be 3-5.
The iron carbon is a powdery iron carbon raw material, and the content of the iron carbon with the granularity of less than 90 mu m is more than 90 percent; fe2O3The content of the effective carbon is controlled to be 25 percent ~ ~ 60 percent and 15 percent ~ 30 percent.
The defluorinating agent is high-purity polyaluminium chloride; the flocculant is polyacrylamide PAM.
The fluorine ion concentration in the sewage is 50mg/L ~ 65mg/L, the water amount is 120L/h, the iron carbon addition amount is 2.8 ~ 3.9.9 g/L, the dosage of polymeric ferric sulfate for acidification is 1500 ~ ~ 1800ppm, the dosage of an active calcium oxide auxiliary agent is 1000 ~ ~ 1500ppm and 1500ppm of a defluorinating agent is 2800 ~ ~ 3428 ppm.
The invention organically combines the micro-electrolysis and chemical precipitation method with the coagulating precipitation method; the method realizes deep fluorine removal through iron-carbon micro-electrolysis on the basis of a chemical precipitation method and a coagulating precipitation method, can effectively control the cost, and has wide market demand in the field of fluorine removal of industrial sewage.
The method comprises the steps of performing acidification pretreatment on sewage, then feeding the sewage into an iron-carbon micro-electrolysis reactor, aerating the reactor for a certain time by adopting air, and then adding active calcium hydroxide to perform chemical fluorine fixation treatment and polyaluminium chloride coagulating sedimentation; or adding polyaluminium chloride in the sewage acidification step according to different sewage, and adding active calcium hydroxide after iron-carbon micro-electrolysis to complete a deep defluorination process; the adjustment can achieve good deep fluorine removal effect.
The invention has low one-time investment and has particularly obvious advantages compared with modes of ion exchange, electric flocculation, electrodialysis and the like; the raw materials are wide in source, low in price and low in running cost; the polymeric ferric sulfate and the like are used for replacing corrosive acid liquid such as sulfuric acid, hydrochloric acid and the like, so that the process operation risk is greatly reduced; the defluorination effect is good, all links are mutually safe, and the effluent fluoride ions can be effectively controlled below 1 mg/L; the method has the advantages of no complicated process flows such as back washing, sewage backflow and the like, less moving equipment in each link, simple production organization and operation, stable and reliable system operation and capability of meeting the requirement of long-period stable operation.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
A gasification system of a certain coal chemical industry company adopts an aerospace furnace, raw material coal is anthracite, the coal quality is poor, the ash melting point is high, the discharge capacity of the existing gasification ash water system is 70 m/h, the fluorine ion index of the discharged water is high, in order to meet the environmental protection requirement, the fluorine ion in the gasification ash water needs to be subjected to key reduction treatment, and the index requirement of 1mg/L is met.
TABLE 1 gasification effluent quality index table
Laboratory beaker test: the test is optimized and verified on the basis of the early-stage basic data test; the addition of iron-carbon microelectrolytic acid is used for testing the influence of pH value on the microelectrolysis effect; adding an auxiliary agent to adjust and optimize on the basis of a predicted reasonable pH value; on the basis of approximate stability of each medicament, the stability of controlling the concentration of the fluorine ions to be 1mg/L is verified; the drug conditions were: the acid is ferric sulfate, the concentration is 30%; the auxiliary agent is active calcium hydroxide; the defluorinating agent is high-purity polyaluminium chloride. The test data are shown in table 2.
Table 2: laboratory beaker experimental data
According to the optimization and verification test of the beaker, the method can stably control the concentration of the fluorine ions to be below 1 mg/L.
A pilot test of a chemical company comprises that a reaction tank is selected to be 120L in a coal chemical industry unit, the hourly water quantity is controlled to be 120L/h, raw water flows out of a sewage sampling port in operation, the water quality is consistent with that of a production system, the fluorine ion concentration is 50mg/L ~ 65mg/L, a test device simulates an on-site production process flow, and the volume of the reaction tank is reduced by 1000 times (the on-site volume is 120 m)3) The method for removing fluorine comprises the following specific steps:
micro-electrolysis, chemical precipitation and coagulating precipitation are combined for removing fluorine; acidifying the sewage to a pH value of 3-5 before the sewage enters a micro-electrolysis reaction tank, arranging iron and carbon in the micro-electrolysis reaction tank, and aerating by using compressed air; adding an active calcium hydroxide auxiliary agent before the micro-electrolyzed sewage enters a coagulating sedimentation reaction tank, adjusting the pH value to be 8.5-9.5, adding a defluorinating agent into the coagulating sedimentation reaction tank, stirring by an aeration device for reaction, and discharging to a simulated clarification tank; and (4) dropping a flocculating agent before the treated water enters a clarification tank, performing flocculation sedimentation in the clarification tank, and taking the supernatant for analysis.
The test uses water for discharging sewage from the 2# tower, the fluorine ion of the raw water is 55mg/L, the xanthate concentration is 20%, the ferric sulfate concentration is 30%, and the test is carried out continuously.
The addition amount of the iron and carbon is 2.8 ~ 3.9.9 g/L (adding once according to 8 hours of water in hours), the use amount of the ferric sulfate is 1500 ~ ~ 1800ppm, the use amount of the auxiliary agent is 1000 ~ ~ 1500ppm, and the addition amount of the polyaluminium chloride is 2800 ~ ~ 3428 ppm.
The pilot test has the effects that the system runs continuously, the concentration of the outlet fluorine ions is sampled and tested once in three hours, and after the debugging is stable, the fluorine ions can be stably controlled to be 0.54 ~ ~ 0.98.98 mg/L.
In conclusion, the method for removing fluorine from industrial sewage can stably reduce the fluorine ion concentration of the industrial sewage with the raw water fluorine ion concentration of more than 50mg/L to less than 1 mg/L. Compared with the particle exchange method such as resin adsorption, the method has the advantages of simple process flow, stable and reliable system and economy, and is a novel defluorination technology which can be popularized and applied.
It is to be noted that, in this document, the terms "comprises", "comprising" or any other variation thereof are intended to cover a non-exclusive inclusion, so that an article or apparatus including a series of elements includes not only those elements but also other elements not explicitly listed or inherent to such article or apparatus. Without further limitation, an element defined by the phrase "comprising … …" does not exclude the presence of additional like elements in the article or device comprising the element.
The above embodiments are merely to illustrate the technical solutions of the present invention and not to limit the present invention, and the present invention has been described in detail with reference to the preferred embodiments. It will be understood by those skilled in the art that various modifications and equivalent arrangements may be made without departing from the spirit and scope of the present invention and it should be understood that the present invention is to be covered by the appended claims.
Claims (7)
1. A defluorination method of industrial sewage is characterized in that: micro-electrolysis, chemical precipitation and coagulating precipitation are combined for removing fluorine; acidifying the sewage to a pH value of 3-5 before the sewage enters a micro-electrolysis reaction tank, arranging iron and carbon in the micro-electrolysis reaction tank, and aerating by using compressed air; adding an active calcium hydroxide auxiliary agent before the micro-electrolyzed sewage enters a coagulating sedimentation reaction tank, adjusting the pH value to be 8.5-9.5, adding a defluorinating agent into the coagulating sedimentation reaction tank, stirring by an aeration device for reaction, and discharging to a clarification tank; and (4) dropping a flocculating agent before the treated water enters a clarification tank, performing flocculation sedimentation in the clarification tank, and taking the supernatant for analysis.
2. The method for removing fluorine from industrial sewage according to claim 1, wherein: the sewage acidification treatment adopts sulfuric acid, hydrochloric acid or other acidic materials.
3. The method for removing fluorine from industrial sewage according to claim 2, wherein: and the sewage acidification treatment adopts polymeric ferric sulfate or polymeric aluminum sulfate for acidification.
4. The method for removing fluorine from industrial sewage according to claim 1, wherein: the iron carbon is semi-coking dry distillation type iron carbon, is added at one time, water enters from the bottom, and the pH value is controlled to be 3-5.
5. The method for removing fluorine from industrial sewage according to claim 4, wherein: the iron carbon is a powdery iron carbon raw material, and the content of the iron carbon with the granularity of less than 90 mu m is more than 90 percent; fe2O3The content of the effective carbon is controlled to be 25 percent ~ ~ 60 percent and 15 percent ~ 30 percent.
6. The method for removing fluorine from industrial sewage according to claim 1, wherein: the defluorinating agent is high-purity polyaluminium chloride; the flocculant is polyacrylamide PAM.
7. The method for removing fluorine from industrial sewage according to claim 1, wherein the concentration of fluorine ions in the sewage is 50mg/L ~ 65mg/L, the water amount is 120L/h, the addition amount of iron and carbon is 2.8 ~ 3.9.9 g/L, the dosage of polymeric ferric sulfate for acidification is 1500 ~ ~ 1800ppm, the dosage of the active calcium oxide auxiliary agent is 1000 ~ ~ 1500ppm, and the dosage of the polymeric aluminum chloride is 2800 ~ ~ 3428 ppm.
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Cited By (1)
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|---|---|---|---|---|
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Cited By (2)
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| CN113480056A (en) * | 2021-08-04 | 2021-10-08 | 湘潭大学 | Method for treating high-concentration fluorine-containing wastewater by two-stage iron-carbon adsorption-complexation-co-coprecipitation process |
| CN113480056B (en) * | 2021-08-04 | 2022-10-25 | 湘潭大学 | Method for treating high-concentration fluorine-containing wastewater by two-stage iron-carbon adsorption-complexation-synergistic co-precipitation process |
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Application publication date: 20191220 |
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